CN113710678A

CN113710678A - Method for preparing catalyst precursor material

Info

Publication number: CN113710678A
Application number: CN202080029443.7A
Authority: CN
Inventors: J·戴瓦拉吉; 张春明; S·D·菲斯特; H·潘; D·W·布雷洛克; I·B·吉莱斯皮; P·L·海德尔; C·S·戴维斯; A·伊冯-贝塞特
Original assignee: Dow Global Technologies LLC
Current assignee: Dow Global Technologies LLC
Priority date: 2019-03-31
Filing date: 2020-03-27
Publication date: 2021-11-26
Also published as: SG11202110593WA; KR20210146976A; US20220251115A1; JP7514253B2; WO2020205525A1; BR112021019414A2; EP3947402A1; JP2022527096A

Abstract

Methods for preparing catalyst precursor materials from dihalo-substituted metalloids are provided. The process comprises mixing in a first reaction zone a first solution consisting of: a haloalkane, at least one solvent and a first component selected from a dihalo-substituted group 14 metal or organolithium reagent. The first solution is continuously added to a second reaction zone, and the second solution is continuously added to the second reaction zone. The second solution comprises at least one solvent and a second component of the dihalo-substituted group 14 metal or the organolithium reagent that is different from the first component. Mixing the first solution and the second solution in the second reaction zone.

Description

Method for preparing catalyst precursor material

Technical Field

The present specification relates generally to methods for preparing catalyst precursor materials from dihalo-substituted metalloids. In particular, the present specification relates to a process for preparing a catalyst precursor material from a dihalogen substituted group 14 metal, a haloalkane, an organolithium reagent and a solvent in a continuous addition reaction.

Background

Linear low density ethylene-based polymers are designed and increasingly used to meet the ever-increasing demand for packaging, hygiene and medical products. Dihalo-substituted metalloids can be used to form reaction catalysts for the production of linear low density ethylene-based polymer resins. However, the solutions used to produce these dihalo-substituted metalloids are susceptible to dissociation even under mild conditions, which makes the production of the dihalo-substituted metalloids difficult and costly.

Current methods for preparing these catalyst precursor materials from dihalo-substituted metalloids require batch reactions, which are thermally unstable and can result in batch-to-batch purity variations. Accordingly, there is a need for alternative processes for producing these catalyst precursor materials. For example, there is a need for a process that can increase the yield and easily and consistently control the temperature of the reactants that form the dihalo-substituted metalloid.

Disclosure of Invention

According to one embodiment, a method comprises: combining a first solution in a first reaction zone, said first solution comprising a haloalkane, at least one solvent, and a first component selected from one of a dihalogen substituted group 14 metal or organolithium reagent; continuously adding the first solution to a second reaction zone; continuously adding a second solution to said second reaction zone, said second solution comprising at least one solvent and a second component selected from one of said dihalosubstituted group 14 metal or said organolithium reagent, wherein said second component is different from said first component; and mixing the first solution and the second solution in the second reaction zone.

According to other embodiments, a method comprises: reacting an organolithium reagent, a haloalkane, and at least one solvent in a first reaction zone to form a first solution; continuously adding the first solution and a second solution to a second reaction zone, wherein the second solution comprises a dihalo-substituted group 14 metal and at least one solvent; and mixing the first solution and the second solution in the second reaction zone.

Additional features and advantages will be set forth in the detailed description which follows, and in part will be readily apparent to those skilled in the art from that description or recognized by practicing the embodiments described herein, including the detailed description which follows, the claims, as well as the appended drawings.

It is to be understood that both the foregoing general description and the following detailed description describe various embodiments, and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter. The accompanying drawings are included to provide a further understanding of the various embodiments, and are incorporated into and constitute a part of this specification. The drawings illustrate various embodiments described herein and together with the description serve to explain the principles and operations of the claimed subject matter.

Drawings

Fig. 1 schematically depicts a system for preparing a catalyst precursor material according to one or more embodiments disclosed and described herein;

fig. 2 schematically depicts an alternative system for preparing a catalyst precursor material, according to one or more embodiments disclosed and described herein; and is

Fig. 3 depicts a Gas Chromatography (GC) spectrum of a catalyst precursor material produced according to one or more embodiments disclosed and described herein.

Detailed Description

Reference will now be made in detail to examples of methods for preparing catalyst precursor materials from dihalo-substituted metalloids. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts.

As used herein, the term "metalloid" refers to a chemical element whose properties are intermediate between those of a metal and a non-metal, or are a mixture of those of a metal and a non-metal.

As used herein, the term "group 14 metal" refers to a metalloid that is a member of group 14 of the IUPAC periodic table. Examples of group 14 metals include, but are not limited to, silicon and germanium.

As used herein, the term "dihalo-substituted group 14 metal" refers to a group 14 metal comprising (a) two halo substituents and (b) two additional substituents. The two halo substituents may include, but are not limited to, fluoro, bromo, chloro, and iodo. The two halo substituents may be the same as each other or may be different from each other. The two further substituents may be identical to one another or may be different from one another. In embodiments, the additional substituents may include, but are not limited to, isopropyl, tert-butyl, hexyl, or combinations thereof.

As used herein, the term "haloalkane" refers to any alkane comprising (a)1 to 3 carbon atoms and (b) at least one halo substituent. The at least one halo substituent may include, but is not limited to, fluoro, bromo, chloro, and iodo. In an embodiment, the halogenated alkane may comprise a dihalomethane.

As used herein, the term "organolithium reagent" refers to any organometallic compound that contains at least one carbon-lithium bond.

As used herein, the term "solvent" includes any substance capable of dissolving one or more of a dihalosubstituted group 14 metal, an organolithium reagent, or a haloalkane. Suitable solvents may include, but are not limited to, any ether solvent, alkyl solvent, or aromatic solvent. The solvent may be present in any of the systems described herein, alone or in any combination.

Examples of suitable ether solvents may include, but are not limited to, tetrahydrofuran, 2-methyltetrahydrofuran, dimethyl ether, t-butyl methyl ether, cyclopentyl methyl ether, and 1, 2-dimethoxyethane.

Examples of suitable alkyl solvents may include, but are not limited to, any alkane containing from 1 carbon atom to 40 carbon atoms. In an embodiment, the alkyl solvent contains 5 to 7 carbon atoms.

Examples of suitable aromatic solvents may include any suitable alkylbenzene compounds. Specific examples suitable aromatic solvents include, but are not limited to, benzene, C₂Benzene, C₃Benzene or C₄Benzene.

In an embodiment, a method for preparing a catalyst precursor material comprises: continuously adding a first solution comprising an organolithium reagent, a haloalkane and at least one solvent to a first reaction zone; mixing said first solution in said first reaction zone; continuously adding said first solution and a second solution comprising a dihalogen substituted group 14 metal and at least one solvent to a second reaction zone; and mixing the first solution and the second solution in the second reaction zone.

In further embodiments, a method for preparing a catalyst precursor material comprises: combining a first solution in a first reaction zone, said first solution comprising a haloalkane, at least one solvent, and a first component selected from one of a dihalogen substituted group 14 metal or organolithium reagent; continuously adding the first solution to a second reaction zone; continuously adding a second solution to said second reaction zone, said second solution comprising at least one solvent and a second component selected from one of said dihalosubstituted group 14 metal or said organolithium reagent, wherein said second component is different from said first component; and mixing the first solution and the second solution in the second reaction zone.

Conventional processes for forming catalyst precursor materials include batch production processes that are carried out in a particular manner. The conventional process comprises preparing a feed solution comprising a dihalo-substituted group 14 metal and a haloalkane in a solvent in a vessel cooled to at least-70 ℃ in an acetone-dry ice bath. The organolithium reagent is added to the vessel over a span of hours, such as 6 hours, ensuring that the organolithium reagent is directed to the vessel wall to cool it before it is mixed with the other reactants. However, such mass production methods often lead to errors, which may be due to unexpected or uncontrolled temperature variations. These errors can result in the purity of the catalyst precursor material being negatively affected.

In contrast, the system of the embodiment shown in fig. 1-3 is a continuous synthesis system in which the reactants are continuously fed into one or more reaction zones. The embodiments depicted in fig. 1-3 described herein provide suitable systems for preparing catalyst precursor materials.

Referring now to fig. 1, a system and method for producing a catalyst precursor material by feeding a continuous stream into a reaction zone is described. In the embodiment of the catalyst precursor material production system 100 shown in fig. 1, the contents of the first reagent feed tank 110 are introduced to the pre-cooler 120 through the first reagent feed stream 112 that fluidly couples the first reagent feed tank 110 to the pre-cooler 120. The first reagent feed tank 110 may comprise any suitable storage device, such as a cooling vessel, optionally with the ability to mix its contents. It should be further understood that the first reagent feed tank 110 and the pre-cooler 120 may be a single, combined physical unit (not shown in fig. 1) or separate physical units fluidly coupled to each other.

A heat exchanger may optionally be added anywhere along the first reagent feed stream 112 to further cool the contents of the first reagent feed tank 110 prior to introducing the contents of the first reagent feed tank 110 to the pre-cooler 120. According to an embodiment, the contents of the first reagent feed tank 110 can comprise a mixture of a dihalo-substituted group 14 metal and a haloalkane, optionally in a solvent. In embodiments, the solvent is an ether solvent, an alkyl solvent, an aromatic solvent, or a combination thereof.

In an embodiment, the dihalo-substituted group 14 metal originally present in the first reagent feed tank 110 in the system may include, but is not limited to, dichlorodiisopropylsilane, di-t-butyldichlorosilane, dichlorodiphenylsilane, dichlorodiisopropylgermane, di-t-butyldichlorogermane, dichlorodiphenylgermane, or combinations thereof. In certain embodiments, the dihalo-substituted group 14 metal present in the first reagent feed tank 110 is dichlorodiisopropylsilane.

In embodiments, the halogenated alkane is also initially present in the first reagent feed tank 110 in the system, or may be added to a pre-cooler 120 in the system (not shown in fig. 1). The haloalkane may be any suitable haloalkane, such as a dihalomethane. Examples of suitable dihalomethanes include, but are not limited to, dibromomethane, dichloromethane, difluoromethane, diiodomethane, bromochloromethane, bromofluoromethane, bromoiodomethane, chlorofluoromethane, chloroiodomethane, fluoroiodomethane, or combinations thereof. In certain embodiments, the halogenated alkane initially present in first reagent feed tank 110 is bromochloromethane.

Once the contents of the pre-cooler 120 (which may include equipment for mixing its components according to embodiments) reach a desired capacity, the contents of the pre-cooler 120 are continuously added to the reaction zone 130 through the feed stream 114 that fluidly couples the pre-cooler 120 to the reaction zone 130.

It should be understood that the concentration of the various components in the first reagent feed tank 110 may be modified by adding solvent to the first reagent feed stream 112, to the precooler 120, or to the feed stream 114 at any point prior to the feed stream 114 being added to the reaction zone 130, such as at the first reagent feed tank 110. Without being bound by theory, it is believed that the dilution of the components, control of the reaction rate, mixing control, and system temperature maintenance are negatively affected if the concentration of the dihalo-substituted group 14 metal and/or haloalkane is too high or too low.

At the same time, the contents of the second reagent feed tank 140 are fed by the second reagent feed stream 116 through the heat exchanger 150, which fluidly couples the second reagent feed tank 140 to the heat exchanger 150. The second reagent feed tank 140 may comprise any suitable storage device, such as a cooling vessel, optionally with the ability to mix any of its contents. It should be further understood that the second reagent feed tank 140 and the heat exchanger 150 may be a single, combined physical unit (not shown in fig. 1) or separate physical units.

Prior to continuous addition to the reaction zone 130, the contents of the feed stream 114 and the feed stream 118 are cooled to a temperature of from 0 ℃ to-90 ℃, as in the pre-cooler 120 and the heat exchanger 150. In an embodiment, feed stream 114 and feed stream 118 are independently cooled to a temperature of-5 ℃ to-90 ℃, such as-10 ℃ to-90 ℃, -15 ℃ to-90 ℃, -20 ℃ to-90 ℃, -25 ℃ to-90 ℃, -30 ℃ to-90 ℃, -35 ℃ to-90 ℃, -40 ℃ to-90 ℃, -45 ℃ to-90 ℃, -50 ℃ to-90 ℃, -55 ℃ to-90 ℃, -60 ℃ to-90 ℃, -65 ℃ to-90 ℃, -70 ℃ to-90 ℃, -75 ℃ to-90 ℃, -80 ℃ to-90 ℃, or-85 ℃ to-90 ℃ before being continuously introduced into reaction zone 130. In some embodiments, feed stream 114 and feed stream 118 are independently cooled to a temperature of 0 ℃ to-85 ℃ prior to being continuously introduced into reaction zone 130, such as 0 ℃ to-80 ℃, 0 ℃ to-75 ℃, 0 ℃ to-70 ℃, 0 ℃ to-65 ℃, 0 ℃ to-60 ℃, 0 ℃ to-55 ℃, 0 ℃ to-50 ℃, 0 ℃ to-45 ℃, 0 ℃ to-40 ℃, 0 ℃ to-35 ℃, 0 ℃ to-30 ℃, 0 ℃ to-25 ℃, 0 ℃ to-20 ℃, 0 ℃ to-15 ℃ or 0 ℃ to-10 ℃. In an embodiment, the feed stream 114 and the feed stream 118 are independently cooled to a temperature of-20 ℃ to-80 ℃, such as-30 ℃ to-70 ℃, -35 ℃ to-65 ℃, -40 ℃ to-60 ℃, or-45 ℃ to-55 ℃ before being continuously introduced into the reaction zone 130. Without being bound by theory, it is believed that the addition of the organolithium reagent to reaction zone 130 causes an exothermic reaction such that the system must be cooled to a suitable temperature to avoid dispersion of one or more of the reactions that occur when the contents are introduced to reaction zone 130 at temperatures outside of the described suitable range. As previously described, the contents entering the reaction zone 130 may be cooled by any suitable cooling device, such as a heat exchanger 150.

According to an embodiment, the contents of the second reagent feed tank 140 comprise an organolithium reagent. In an embodiment, the organolithium reagent initially present in the second reagent feed tank 140 in the system can comprise any suitable organolithium reagent. Examples of suitable organolithium reagents can include, but are not limited to, n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, or combinations thereof. In certain embodiments, the organolithium reagent initially present in the second reagent feed tank 140 is n-butyllithium.

Optionally, an amount of solvent may be added to the second reagent feed tank 140 and/or at any point along the second reagent feed stream 116 to dilute the organolithium reagent fed to the heat exchanger 150. Once the second reagent feed stream 116 passes through the heat exchanger 150, it is fed to the reaction zone 130 through the cooled feed stream 118 that fluidly couples the heat exchanger 150 with the reaction zone 130. In embodiments, the solvent is an ether solvent, an alkyl solvent, an aromatic solvent, or a combination thereof.

If excess organolithium reagent passes through the second reagent feed stream 116 and is distributed to other components of the system (e.g., the reaction zone 130), a quench tank 122 comprising a quench agent, such as ammonium chloride, can optionally be provided at any point along the second reagent feed stream 116, thereby causing process upsets. However, the quench tank 122 is only an optional component in the catalyst precursor material production system 100 shown in fig. 1 and does not affect the purity of the product produced by the catalyst precursor material production system 100. It is to be understood that in some embodiments, a quenching agent may be added to any component of the precursor material production system 100 (e.g., the pre-cooler 120, the heat exchanger 150, or the reaction zone 130) as needed to quench the reaction. However, some embodiments do not include quenching.

After the contents of the first reagent feed tank 110 and the second reagent feed tank 140 have been continuously added to the reaction zone 130, the contents of the reaction zone 130 are mixed to produce the catalyst precursor material 160. The conditions of the reaction zone 130 are maintained at a temperature of from 0 ℃ to-90 ℃ and the residence time of the contents in the reaction zone 130 is from 0.1 seconds to 120 minutes. Without being bound by theory, it is believed that the temperature range of the reaction zone 130 allows for the production of the desired product by the catalyst precursor material 160 produced by such methods. Suitable reaction zone 130 equipment may include, but is not limited to, a tubular reactor or a stirred tank reactor. In an embodiment, the catalyst precursor material production system 100 can further comprise a nitrogen blanket, one or more thermocouples, and/or a sampling port.

In an embodiment, the reaction zone 130 is cooled during the continuous addition of any of the contents of the first reagent feed tank 110 and/or the second reagent feed tank 140. In an embodiment, the temperature of reaction zone 130 during continuous introduction of the contents is from 0 ℃ to-90 ℃ and all ranges and subranges therebetween. In the examples, the temperature of the reaction zone 130 is from-5 ℃ to-90 ℃, such as from-10 ℃ to-90 ℃, from-15 ℃ to-90 ℃, from-20 ℃ to-90 ℃, from-25 ℃ to-90 ℃, from-30 ℃ to-90 ℃, from-35 ℃ to-90 ℃, from-40 ℃ to-90 ℃, from-45 ℃ to-90 ℃, from-50 ℃ to-90 ℃, from-55 ℃ to-90 ℃, from-60 ℃ to-90 ℃, from-65 ℃ to-90 ℃, from-70 ℃ to-90 ℃, from-75 ℃ to-90 ℃, from-80 ℃ to-90 ℃, or from-85 ℃ to-90 ℃. In some embodiments, the temperature of the reaction zone 130 is from 0 ℃ to-85 ℃, such as from 0 ℃ to-80 ℃, from 0 ℃ to-75 ℃, from 0 ℃ to-70 ℃, from 0 ℃ to-65 ℃, from 0 ℃ to-60 ℃, from 0 ℃ to-55 ℃, from 0 ℃ to-50 ℃, from 0 ℃ to-45 ℃, from 0 ℃ to-40 ℃, from 0 ℃ to-35 ℃, from 0 ℃ to-30 ℃, from 0 ℃ to-25 ℃, from 0 ℃ to-20 ℃, from 0 ℃ to-15 ℃ or from 0 ℃ to-10 ℃. In the examples, the temperature of the reaction zone 130 is from-20 ℃ to-80 ℃, such as from 30 ℃ to-70 ℃, -from 35 ℃ to-65 ℃, -from 40 ℃ to-60 ℃, or-from 45 ℃ to-55 ℃. Without being bound by theory, it is believed that the described temperature range of the reaction zone 130 allows for the production of suitable catalyst precursor materials. The reaction zone 130 may be cooled by any suitable means.

Based on the previously described examples, the residence time of the contents of the reaction zone 130 may be in the range of 0.1 seconds to 120 minutes, and all ranges and subranges therebetween. The term "residence time" is defined herein as the average time any one or more of the contents remain in the reaction zone. The residence time is measured by dividing the reaction zone volume by the total volumetric flow rate of any one or more of the one or more contents in the reaction zone. In an embodiment, the residence time of the contents in reaction zone 130 ranges from 1 second to 120 minutes, 10 seconds to 120 minutes, 30 seconds to 120 minutes, 1 minute to 120 minutes, 5 minutes to 110 minutes, 10 minutes to 100 minutes, 20 minutes to 90 minutes, 25 minutes to 75 minutes, 30 minutes to 70 minutes, 35 minutes to 65 minutes, 40 minutes to 60 minutes, 0.1 second to 30 minutes, 0.1 second to 10 minutes, 0.1 second to 5 minutes, 0.1 second to 1 minute, 0.1 second to 30 seconds, 1 second to 10 minutes, 1 second to 5 minutes, 1 second to 1 minute, or 1 second to 30 seconds. In some embodiments, the residence time of the contents in reaction zone 130 ranges from 0.1 seconds to 30 seconds, such as from 0.1 seconds to 25 seconds, from 0.1 seconds to 20 seconds, from 0.1 seconds to 15 seconds, from 0.1 seconds to 10 seconds, from 0.1 seconds to 5 seconds, from 0.1 seconds to 1 second, or from 0.1 seconds to 0.5 seconds.

The reaction between the dihalogen substituted group 14 metal, the haloalkane, and the organolithium in the reaction zone 130 is exothermic. Thus, in some embodiments, a mixture of dihalo-substituted group 14 metals and/or organolithium can be optionally quenched in the reaction zone 130 with any suitable quenching agent. However, in the method for producing the catalyst precursor material of the example, quenching any of the components in the reaction zone 130 is not a necessary step.

Referring now to fig. 2, additional systems and methods for producing catalyst precursor materials by introducing a continuous flow stream into a reaction zone are described. In the embodiment of the catalyst precursor material production system 300 shown in fig. 2, the contents of the first reagent feed tank 310 are introduced to the optional heat exchanger 320 via the first reagent feed stream 312 that fluidly couples the first reagent feed tank 310 with the optional heat exchanger 320. The first reagent feed tank 310 may comprise any suitable storage device, such as a cooling vessel, optionally with the ability to mix any of its contents. It should be further understood that the first reagent feed tank 310 and the optional heat exchanger 320 may be a single, combined physical unit or separate physical units fluidly coupled to each other.

Heat exchanger 320 may optionally be added anywhere along first reagent feed stream 312 to cool the contents of first reagent feed tank 310 before their introduction to first reaction zone 330 via cooled first reagent feed stream 314. According to an embodiment, the contents of the first reagent feed tank 310 may comprise an organolithium reagent, optionally in a solvent. Heat exchanger 320 can be any heat exchanger capable of reducing first reagent feed stream 312 to a temperature from 0 ℃ to-90 ℃.

In an embodiment, the organolithium reagent initially present in the first reagent feed tank 310 in the system can comprise any suitable organolithium reagent. Examples of suitable organolithium reagents can include, but are not limited to, n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, or combinations thereof. In certain embodiments, the organolithium reagent initially present in the first reagent feed tank 310 is n-butyllithium.

Optionally, an amount of solvent may be added to the first reagent feed tank 310 and/or at any point along the first reagent feed stream 312 and/or at any point along the cooled first reagent feed stream 314 to dilute the organolithium reagent being fed to the first reaction zone 330. In embodiments, the solvent is an ether solvent, an alkyl solvent, an aromatic solvent, or a combination thereof.

At the same time, the contents of the second reagent feed tank 340 are fed by the second reagent feed stream 316 through the optional heat exchanger 350, which fluidly couples the second reagent feed tank 340 to the optional heat exchanger 350. The second reagent feed tank 340 may comprise any suitable storage device, such as a cooling vessel, optionally with the ability to mix any of its contents. It should be further understood that the second reagent feed tank 340 and the optional heat exchanger 350 may be a single, combined physical unit, or separate physical units.

An optional heat exchanger 350 may optionally be added anywhere along the second reagent feed stream 314 to cool the contents of the second reagent feed tank 340 to a temperature in the range of from 0 ℃ to-90 ℃ before the contents are introduced to the first reaction zone 330 by the cooled second reagent feed stream 318. According to an embodiment, the contents of the second reagent feed tank 340 may comprise a haloalkane, optionally in a solvent. Optionally, an amount of solvent may be added to the second reagent feed tank 340 and/or at any point along the second reagent feed stream 314 and/or at any point along the cooled second reagent feed stream 316 to dilute the haloalkane fed to the first reaction zone 330.

In an embodiment, the halogenated alkane also initially present in second reagent feed tank 340 in system 300 can comprise any suitable halogenated alkane, such as a dihalomethane. Examples of suitable dihalomethanes include, but are not limited to, dibromomethane, dichloromethane, difluoromethane, diiodomethane, bromochloromethane, bromofluoromethane, bromoiodomethane, chlorofluoromethane, chloroiodomethane, fluoroiodomethane, or combinations thereof. In certain embodiments, the halogenated alkane initially present in second reagent feed tank 340 is bromochloromethane.

The contents of the first reagent feed tank 310 and optionally the second reagent feed tank 340 are cooled to a temperature of from 0 ℃ to-90 ℃ prior to being continuously introduced into the first reaction zone 330. In the examples, the contents of the first reagent feed tank 310 and optionally the second reagent feed tank 340 are cooled to a temperature of-5 ℃ to-90 ℃, such as-10 ℃ to-90 ℃, -15 ℃ to-90 ℃, -20 ℃ to-90 ℃, -25 ℃ to-90 ℃, -30 ℃ to-90 ℃, -35 ℃ to-90 ℃, -40 ℃ to-90 ℃, -45 ℃ to-90 ℃, -50 ℃ to-90 ℃, -55 ℃ to-90 ℃, -60 ℃ to-90 ℃, -65 ℃ to-90 ℃, -70 ℃ to-90 ℃, -75 ℃ to-90 ℃, -80 ℃ to-90 ℃ or-85 ℃ to-90 ℃. In some embodiments, the contents of the first reagent feed tank 310 and optionally the second reagent feed tank 340 are cooled to a temperature of from 0 ℃ to-85 ℃, such as from 0 ℃ to-80 ℃, from 0 ℃ to-75 ℃, from 0 ℃ to-70 ℃, from 0 ℃ to-65 ℃, from 0 ℃ to-60 ℃, from 0 ℃ to-55 ℃, from 0 ℃ to-50 ℃, from 0 ℃ to-45 ℃, from 0 ℃ to-40 ℃, from 0 ℃ to-35 ℃, from 0 ℃ to-30 ℃, from 0 ℃ to-25 ℃, from 0 ℃ to-20 ℃, from 0 ℃ to-15 ℃ or from 0 ℃ to-10 ℃. In an embodiment, the contents of the first reagent feed tank 310 and optionally the second reagent feed tank 340 are cooled to a temperature of-20 ℃ to-80 ℃, such as-30 ℃ to-70 ℃, -35 ℃ to-65 ℃, -40 ℃ to-60 ℃ or-45 ℃ to-55 ℃. Without being bound by theory, it is believed that the addition of the organolithium reagent to first reaction zone 330 causes an exothermic reaction such that the system must be cooled to a suitable temperature to avoid dispersion of one or more of the reactions that occur when the contents are introduced to first reaction zone 330 at temperatures outside of the suitable ranges described. As previously described, the contents entering the first reaction zone 330 may be cooled by any suitable cooling device, such as a heat exchanger.

Once the contents of first reagent feed tank 310 and second reagent feed tank 340 are introduced into first reaction zone 330, it is believed that the organolithium reagent lithiates the haloalkane in a lithiation reaction. Without being bound by theory, it is believed that lithiating the haloalkane in the first reaction zone 330 can improve the purity and yield of the catalyst precursor material produced by the catalyst precursor material production system 300 shown in fig. 2.

After the contents of the first and second reagent feed tanks 310, 340 have been introduced to the first reaction zone 330, the contents of the first reaction zone 330 are mixed to produce the intermediate catalyst precursor material 326. The conditions of the first reaction zone 330 are maintained at a temperature of from 0 ℃ to-90 ℃ and the residence time of its contents in the first reaction zone 330 is from 0.1 seconds to 120 minutes. Without being bound by theory, it is believed that the temperature range of the first reaction zone 330 allows for the production of the desired end product by the intermediate catalyst precursor material 326 produced by such methods. Suitable first reaction zone 330 equipment may include, but is not limited to, a tubular reactor or a stirred tank reactor. In an embodiment, the catalyst precursor material production system 300 can further comprise a nitrogen blanket, one or more thermocouples, and/or a sampling port.

Once catalyst precursor material 326 has been produced and cooled to a suitable temperature, the catalyst precursor material is then introduced into second reaction zone 380. In an embodiment, the conditions of the second reaction zone 380 are the same as the first reaction zone 330. In other embodiments, the conditions of the second reaction zone 380 are different from the first reaction zone 330.

At the same time, the contents of the third reagent feed tank 360 are fed by the third reagent feed stream 322 through the optional heat exchanger 370, which second reagent feed stream fluidly couples the third reagent feed tank 360 to the optional heat exchanger 370. The third reagent feed tank 360 may comprise any suitable storage device, such as a cooling vessel, optionally with the ability to mix any of its contents. It should be further understood that the third reagent feed tank 360 and the optional heat exchanger 370 may be combined physical units or separate physical units.

An optional heat exchanger 370 may be added anywhere along the second reagent feed stream 322 to cool the contents of the third reagent feed tank 360 to a temperature of from 0 ℃ to-90 ℃ before the contents are introduced to the second reaction zone 370 through the cooled third reagent feed stream 324. According to an embodiment, the contents of the third reagent feed tank 360 can comprise a dihalo-substituted group 14 metal, optionally in a solvent. Optionally, an amount of solvent may be added to the third reagent feed tank 360 and/or at any point along the third reagent feed stream 322 and/or at any point along the cooled third reagent feed stream 324 to dilute the dihalogen-substituted group 14 metal fed to the second reaction zone 380.

In embodiments, the dihalo-substituted group 14 metal may include, but is not limited to, dichlorodiisopropylsilane, di-t-butyldichlorosilane, dichlorodiphenylsilane, dichlorodiisopropylgermane, di-t-butyldichlorogermane, dichlorodiphenylgermane, or combinations thereof. In certain embodiments, the dihalo-substituted group 14 metal is dichlorodiisopropylsilane.

It is to be understood that the concentration of the various components in the first reagent feed tank 310 and/or the second reagent feed tank 340 can be modified by adding solvent at any point prior to adding the first reagent feed stream 314 and/or the second reagent feed stream 318 to the first reaction zone 330, or at any point prior to adding the precursor vapor 326 to the second reaction zone 380. Likewise, the concentration of the component in the third reagent feed tank 360 can be modified by adding the solvent at any point prior to the reagent feed stream 324 being added to the second reaction zone 380. Without being bound by theory, it is believed that the dilution of the components, control of the reaction rate, mixing control, and system temperature maintenance are negatively affected if the concentration of the dihalo-substituted group 14 metal and/or haloalkane is too high or too low.

In an embodiment, the first reaction zone 330 and/or the second reaction zone 380 are cooled during the described process. In an embodiment, the temperature of the first reaction zone 330 and/or the second reaction zone 380 during continuous introduction of the contents is from 0 ℃ to-90 ℃ and all ranges and subranges therebetween. In an embodiment, the temperature of the first reaction zone 330 and/or the second reaction zone 380 is from-5 ℃ to-90 ℃, such as from-10 ℃ to-90 ℃, -15 ℃ to-90 ℃, -20 ℃ to-90 ℃, -25 ℃ to-90 ℃, -30 ℃ to-90 ℃, -35 ℃ to-90 ℃, -40 ℃ to-90 ℃, -45 ℃ to-90 ℃, -50 ℃ to-90 ℃, -55 ℃ to-90 ℃, -60 ℃ to-90 ℃, -65 ℃ to-90 ℃, -70 ℃ to-90 ℃, -75 ℃ to-90 ℃, -80 ℃ to-90 ℃, or-85 ℃ to-90 ℃. In some embodiments, the temperature of the first reaction zone 330 and/or the second reaction zone 380 is from 0 ℃ to-85 ℃, such as from 0 ℃ to-80 ℃, from 0 ℃ to-75 ℃, from 0 ℃ to-70 ℃, from 0 ℃ to-65 ℃, from 0 ℃ to-60 ℃, from 0 ℃ to-55 ℃, from 0 ℃ to-50 ℃, from 0 ℃ to-45 ℃, from 0 ℃ to-40 ℃, from 0 ℃ to-35 ℃, from 0 ℃ to-30 ℃, from 0 ℃ to-25 ℃, from 0 ℃ to-20 ℃, from 0 ℃ to-15 ℃ or from 0 ℃ to-10 ℃. In an embodiment, the temperature of the first reaction zone 330 and/or the second reaction zone 380 is from-20 ℃ to-80 ℃, such as from 30 ℃ to-70 ℃, -35 ℃ to-65 ℃, -40 ℃ to-60 ℃, or-45 ℃ to-55 ℃. Without being bound by theory, it is believed that the described temperature ranges of the first reaction zone 330 and/or the second reaction zone 380 allow for the production of the desired product by the catalyst precursor materials produced by the methods described herein. The first reaction zone 330 and/or the second reaction zone 380 may be cooled by any suitable means.

Based on the previously described embodiments, the residence time of the contents of first reaction zone 330 and/or second reaction zone 380 may be in the range of 0.1 seconds to 120 minutes, and all ranges and subranges therebetween. The term "residence time" is defined herein as the average time a fluid stream is maintained in the first reaction zone 330 and/or the second reaction zone 380. The residence time is measured by dividing the reaction zone volume by the total volumetric flow rate of fluid in the reaction zone. In embodiments, the residence time of the contents in first reaction zone 330 and/or second reaction zone 380 ranges from 1 second to 120 minutes, 10 seconds to 120 minutes, 30 seconds to 120 minutes, 1 minute to 120 minutes, 5 minutes to 110 minutes, 10 minutes to 100 minutes, 20 minutes to 90 minutes, 25 minutes to 75 minutes, 30 minutes to 70 minutes, 35 minutes to 65 minutes, 40 minutes to 60 minutes, 0.1 second to 30 minutes, 0.1 second to 10 minutes, 0.1 second to 5 minutes, 0.1 second to 1 minute, 0.1 second to 30 seconds, 1 second to 10 minutes, 1 second to 5 minutes, 1 second to 1 minute, or 1 second to 30 seconds. In some embodiments, the residence time of the contents in first reaction zone 330 and/or second reaction zone 380 ranges from 0.1 seconds to 30 seconds, such as from 0.1 seconds to 25 seconds, from 0.1 seconds to 20 seconds, from 0.1 seconds to 15 seconds, from 0.1 seconds to 10 seconds, from 0.1 seconds to 5 seconds, from 0.1 seconds to 1 second, or from 0.1 seconds to 0.5 seconds.

The reaction between the dihalogen substituted group 14 metal, the haloalkane, and the organolithium in the second reaction zone 380 is exothermic. Thus, in some embodiments, the mixture in the second reaction zone 380 can optionally be quenched with a suitable quenching agent. However, in the method for forming the catalyst precursor material of the embodiments, quenching any of the components in the second reaction zone 380 is not a necessary step.

Further, if an excess of dihalo-substituted group 14 metal-and/or organolithium reagent is passed through the system 300, a quench tank (not shown in fig. 2) containing a quench agent, such as ammonium chloride, can optionally be provided at any point in the catalyst precursor material production system 300, thereby causing process upsets. However, the quench tank is only an optional component in the catalyst precursor material production system 300 shown in fig. 2 and does not affect the purity of the catalyst precursor material 390 produced by the catalyst precursor material production system 300.

The methods described herein are suitable for preparing various catalyst precursor materials for preparing catalysts useful in the production of linear low density ethylene-based polymers. Such catalysts are described in detail in WO 2018/022975 and WO 2018/083056, which are incorporated herein by reference.

By way of example, but not limitation, according to embodiments, catalyst precursor materials may be used to produce representative catalysts as shown in formula (I):

in embodiments of formula (I), M is titanium, zirconium, or hafnium, each independently in a formal oxidation state of +2, +3, or + 4; x is a group 14 metal; r₁Is isopropyl, tert-butyl or hexyl; and R is₂Is isopropyl, tert-butyl or hexyl. In the examples, R₁And R₂Are identical to each other. In other embodiments, R₁And R₂Are different from each other.

According to the examples, formula (I) is merely illustrative of catalysts that can be prepared from various catalyst precursor materials. It does not limit the scope of catalysts that can be prepared from the various catalyst precursor materials described herein.

Examples of the invention

The embodiments are further illustrated by the following examples.

Example 1

A first reagent feed tank was charged with 187 grams (g) dichlorodiisopropylsilane (DCDIS), 388g Bromochloromethane (BCM), and 1,781g Tetrahydrofuran (THF) under nitrogen (N)₂) Mixing under the layer. The first reagent feed tank is connected to the pre-cooler by a conduit. 800 milliliters (mL) of 1.6 moles (M) of hexane were introduced into the tube. The vacuum pushed the contents of the tubing across the first heat exchanger (i.e., a coil immersed in a bath filled with dry ice and acetone) and into the precooler at a flow rate of 1.2mL per minute (1.2 mL/min). Once the contents of the tubing are introduced into the pre-cooler,the stirrer in the pre-cooler began mixing its contents at 740 revolutions per minute (rpm). After the pre-cooler has reached its desired capacity, its contents are introduced into the reaction zone through an additional conduit fluidly connecting the pre-cooler and the reaction zone.

Once the pre-cooler began to flow into the reaction zone, the agitator in the reaction zone began to mix the incoming contents at 740 rpm. When the temperature of the reaction zone reached-75 ℃, n-butyllithium (n-BuLi) was introduced into the reaction zone from the second reagent feed tank at a flow rate of 0.71 ml/min after being cooled by the second heat exchanger. The second reagent feed tank is fluidly connected to the reaction zone by a conduit. The temperature of the reaction zone is maintained at about-70 ℃ during the duration of the synthesis of the catalyst precursor material.

The average residence time of the contents of the reaction zone before collection in the product vessel was 50 minutes. The reaction zone was operated-and catalyst precursor material was collected-for 30 hours. After 30 hours, the n-butyllithium was transferred to the quench tank and the line was flushed with hexane to clear the system of any residual lithiated species.

The conditions for the continuous synthesis of the catalyst precursor material are provided in table 1:

TABLE 1

Parameter(s)	Value of
		Residence time	50 minutes
Concentration of DCDIS	8wt.％
		BCM is equivalent to DCDIS	3.0
N-butyllithium equivalent to DCDIS	2.5
		Temperature of reaction zone	-70℃
Volume of reaction zone	100mL

Three samples were collected during the 30 hour operating period. The purity of each sample was tested using a Gas Chromatograph (GC). Specifically, the purity of the sample is calculated by measuring the ratio of the GC area of the desired product to any undesired product. The purity of each of these samples is provided in table 2:

TABLE 2

Sample source	GC purity
		S1: reaction zone (hour 8)	96.62％
S2: product container 1 (first 20 hours collection)	64.55％
		S3: product container 2 (last 10 hours collection)	93.29％

The first sample (S1) was taken directly from the reaction zone after eight hours of continuous operation, indicating that its purity was high to confirm that the catalyst precursor material described was produced. A GC sample of S1 (as shown in fig. 3) indicated a purity of 96.62%.

A second sample (S2) is taken from a first product container containing catalyst precursor material produced during the first 20 hours of operation. GC samples produced from S2 showed 64.55% purity.

A third sample (S3) is taken from a second product container containing catalyst precursor material produced during the last 10 hours of operation. The GC sample produced from S3 indicated a purity of 93.29%.

Overall, the cumulative purity of the collected catalyst precursor material samples was calculated to be 81.84%.

However, the purity of the catalyst precursor material S3 increased by 28.74% from hour 20 to hour 30. This trend of increasing purity indicates that the longer the system is continuously in use, the more pure the catalyst precursor material becomes according to the examples described herein. Thus, the results confirm that the system described in the present disclosure is suitable for producing catalyst precursor materials in a continuous flow reaction.

Example 2

The first reagent stream was generated by pre-cooling a mixture of Chloroiodomethane (CIM) and THF to-50 ℃. At the same time, a second reagent stream of 2.5M n-butyllithium in hexane was pre-cooled to-50 ℃. Precooling is achieved by a separate heat exchanger (i.e. insertion of tubing into a circulating bath with cooling silicone oil) and deposition into the first reaction zone where mixing lasts from 0.15 to 0.3 seconds before being discharged into the second reaction zone. The third reagent stream containing DCDIS and THF was pre-cooled to-50 ℃ with a heat exchanger. The third reagent stream is then discharged to a second reaction zone where its contents are mixed with the contents of the first reaction zone.

The conditions for the continuous synthesis of the catalyst precursor material are provided in table 3:

TABLE 3

Parameter(s)	Value of
		Residence time in the first reaction zone	0.15 second to 0.3 second
Total flow rate	56 ml per minute
		CIM is equivalent to DCDIS	6.75
N-butyllithium equivalent to DCDIS	2.25
		Temperature of	-50℃
Pressure in the second reaction zone	200 pounds per square inch

During the 6 hour operating period, two samples were collected using the parameters specified above. The purity of the samples was tested using a Gas Chromatograph (GC). Specifically, the purity of the sample is calculated by measuring the ratio of the GC area of the desired product to any undesired product. The results for the samples are provided in table 4 below:

TABLE 4

Parameter(s)	Results
		Purity of sample 1	94％
Purity of sample 2	85％
		Isolated product yield	71％

Thus, the results confirm that the system described in the present disclosure is suitable for producing catalyst precursor materials in a continuous flow reaction.

In a first aspect of the disclosure, a method comprises: reacting an organolithium reagent, a haloalkane, and at least one solvent in a first reaction zone to form a first solution; continuously adding the first solution and a second solution to a second reaction zone, wherein the second solution comprises a dihalo-substituted group 14 metal and at least one solvent; and mixing the first solution and the second solution in the second reaction zone.

A second aspect of the present disclosure may include the first aspect further comprising separately cooling the organolithium reagent and the haloalkane of the first solution to a temperature of from 0 ℃ to-90 ℃ prior to continuously adding the first solution to the first reaction zone.

A third aspect of the present disclosure may include the first or second aspect, wherein the dihalo-substituted group 14 metal includes dichlorodiisopropylsilane, di-t-butyldichlorosilane, dichlorodiphenylsilane, dichlorodiisopropylgermane, di-t-butyldichlorogermane, dichlorodiphenylgermane, or a combination thereof.

A fourth aspect of the present disclosure may include any of the first to third aspects, wherein the organolithium reagent comprises n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, or a combination thereof.

A fifth aspect of the present disclosure may comprise any of the first to fourth aspects, wherein the haloalkane comprises a dihalomethane, preferably bromochloromethane or chloroiodomethane.

A sixth aspect of the present disclosure may include any of the first to fifth aspects, wherein the at least one solvent comprises an ether solvent, an alkyl solvent, an aromatic solvent, or a combination thereof.

A seventh aspect of the present disclosure may include any of the first to sixth aspects, wherein the at least one solvent comprises tetrahydrofuran, hexane, or a combination thereof.

An eighth aspect of the present disclosure may include any of the first to seventh aspects, wherein the first solution is cooled to a temperature of from 0 ℃ to-90 ℃ prior to continuously adding the first solution to the second reaction zone.

A ninth aspect of the present disclosure may include any of the first to eighth aspects, wherein the temperature of the first reaction zone and the second reaction zone is from-40 ℃ to-70 ℃.

In a tenth aspect of the disclosure, a method comprises: combining a first solution in a first reaction zone, said first solution comprising a haloalkane, at least one solvent, and a first component selected from one of a dihalogen substituted group 14 metal or organolithium reagent; continuously adding the first solution to a second reaction zone; continuously adding a second solution to said second reaction zone, said second solution comprising at least one solvent and a second component selected from one of said dihalosubstituted group 14 metal or said organolithium reagent, wherein said second component is different from said first component; and mixing the first solution and the second solution in the second reaction zone.

An eleventh aspect of the present disclosure includes the tenth aspect wherein the first component is the dihalo-substituted group 14 metal and the second component is the organolithium reagent.

A twelfth aspect of the present disclosure includes the tenth aspect, wherein the first component is the organolithium reagent and the second component is the dihalo-substituted group 14 metal.

A thirteenth aspect of the present disclosure includes any of the tenth to twelfth aspects, wherein the dihalo-substituted group 14 metal includes dichlorodiisopropylsilane, di-t-butyldichlorosilane, dichlorodiphenylsilane, dichlorodiisopropylgermane, di-t-butyldichlorogermane, dichlorodiphenylgermane, or a combination thereof.

A fourteenth aspect of the present disclosure includes any of the tenth through thirteenth aspects, wherein the organolithium reagent comprises n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, or a combination thereof.

A fifteenth aspect of the present disclosure includes any of the tenth to fourteenth aspects, wherein the haloalkane comprises a dihalomethane, preferably chloroiodomethane or bromochloromethane.

A sixteenth aspect of the present disclosure includes any of the tenth to fifteenth aspects, wherein the at least one solvent comprises an ether solvent, an alkyl solvent, an aromatic solvent, or a combination thereof.

A seventeenth aspect of the present disclosure includes any of the tenth to sixteenth aspects, wherein the at least one solvent comprises tetrahydrofuran, hexane, or a combination thereof.

An eighteenth aspect of the present disclosure includes any of the tenth to seventeenth aspects, wherein the first solution and the second solution are cooled to at least-70 ℃ prior to continuously adding the first solution and the second solution to the reaction zone.

A nineteenth-eighteenth aspect of the present disclosure includes any of the tenth to eighteenth aspects, wherein the temperature of the reaction zone is from 0 ℃ to-90 ℃, preferably wherein the temperature of the reaction zone is from-40 ℃ to-70 ℃.

It will be apparent to those skilled in the art that various modifications and variations can be made to the embodiments described herein without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the present specification cover the modifications and variations of the various embodiments described herein provided they come within the scope of the appended claims and their equivalents.

Claims

1. A method, comprising:

combining a first solution in a first reaction zone, said first solution comprising a haloalkane, at least one solvent, and a first component selected from one of a dihalogen substituted group 14 metal or organolithium reagent;

continuously adding the first solution to a second reaction zone;

continuously adding a second solution to said second reaction zone, said second solution comprising at least one solvent and a second component selected from one of said dihalosubstituted group 14 metal or said organolithium reagent, wherein said second component is different from said first component; and

mixing the first solution and the second solution in the second reaction zone.

2. The method of claim 1, wherein the first component is the dihalo-substituted group 14 metal and the second component is the organolithium reagent.

3. The process of claim 1 wherein the first component is the organolithium reagent and the second component is the dihalo-substituted group 14 metal.

4. The method of any one of the preceding claims, wherein the dihalo-substituted group 14 metal comprises dichlorodiisopropylsilane, di-t-butyldichlorosilane, dichlorodiphenylsilane, dichlorodiisopropylgermane, di-t-butyldichlorogermane, dichlorodiphenylgermane, or a combination thereof.

5. The process of any one of the preceding claims, wherein the organolithium reagent comprises n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, or a combination thereof.

6. The method of any preceding claim, wherein the haloalkane comprises a dihalomethane.

7. The process of any one of the preceding claims, wherein the temperature of the reaction zone is from 0 ℃ to-90 ℃.

8. A method, comprising:

reacting an organolithium reagent, a haloalkane, and at least one solvent in a first reaction zone to form a first solution;

continuously adding the first solution and a second solution to a second reaction zone, wherein the second solution comprises a dihalo-substituted group 14 metal and at least one solvent; and

mixing the first solution and the second solution in the second reaction zone.

9. The process of claim 8, further comprising separately cooling the organolithium reagent and the haloalkane of the first solution to a temperature of from 0 ℃ to-90 ℃ prior to continuously adding the first solution to the first reaction zone.

10. The method of claim 8 or 9, wherein the dihalo-substituted group 14 metal comprises dichlorodiisopropylsilane, di-t-butyldichlorosilane, dichlorodiphenylsilane, dichlorodiisopropylgermane, di-t-butyldichlorogermane, dichlorodiphenylgermane, or a combination thereof.

11. The process of any one of claims 8-10, wherein the organolithium reagent comprises n-butyllithium, sec-butyllithium, tert-butyllithium, methyllithium, or a combination thereof.

12. The method of any one of claims 8-11, wherein the halogenated alkane comprises a dihalomethane.

13. The method of any one of claims 8 to 12, wherein the at least one solvent comprises an ether solvent, an alkyl solvent, an aromatic solvent, or a combination thereof.

14. The process of any one of claims 8 to 13, wherein the first solution is cooled to a temperature of from 0 ℃ to-90 ℃ prior to continuously adding the first solution to the second reaction zone.

15. The process of any one of claims 8 to 14, wherein the temperature of at least one of the first reaction zone and the second reaction zone is from-40 ℃ to-70 ℃.